KR20180087122A - Concentration monitoring apparatus for developing solution and developing solution management apparatus - Google Patents

Abstract

The present invention provides a developing solution concentration monitoring device for measuring concentration of carbon dioxide absorbed into a developing solution showing alkalinity, and a developing solution management device for managing concentration of carbon dioxide absorbed into the developing solution showing alkalinity. The developing solution concentration monitoring device and the developing solution management device include a densitometer and measure density of the developing solution. There is a good corresponding relationship between density of the developing solution and concentration of the absorbed carbon dioxide regardless of concentrations of other components such as alkali components or the like. The concentration monitoring device calculates concentration of the absorbed carbon dioxide from the corresponding relationship between the density of the developing solution and the concentration of the absorbed carbon dioxide in accordance with measured density values. A warning device emits a warning when concentration values of the carbon dioxide absorbed into the developing solution calculated by a calculating means are deviated from a preset management range. The developing solution management device manages the concentrations of carbon dioxide absorbed into the developing solution by supplying a supplementary solution to the developing solution so that concentrations of carbon dioxide absorbed into the developing solution become a predetermined management value or not more than the management value in accordance with the measured density values or the calculated concentration values of the carbon dioxide absorbed into the developing solution by using the corresponding relationship between the density of the developing solution and the concentration of the absorbed carbon dioxide.

Description

TECHNICAL FIELD [0001] The present invention relates to a developer concentration monitoring apparatus and a developer concentration monitoring apparatus,

The present invention relates to an apparatus for monitoring the concentration of alkaline developer used for developing a photoresist film in a semiconductor or liquid crystal panel and a developing process of a circuit board, and a developer management apparatus.

Description of the Related Art [0002] In a photolithography process for realizing fine wiring in a semiconductor or a liquid crystal panel, a developer (hereinafter referred to as " alkaline solution ") is used as a chemical solution for dissolving a photoresist film- Developing solution ") is used.

BACKGROUND ART [0002] In recent semiconductor and liquid crystal panel substrate manufacturing processes, miniaturization of wafers and glass substrates, miniaturization of wiring processing, and high integration have been progressed. In such a situation, it has become necessary to measure the concentration of the main components of the alkaline developer at a high level of accuracy and to maintain the developer in order to realize miniaturization and high integration of wiring processing on a large substrate.

The measurement of the component concentration of the conventional alkaline developer is carried out in such a manner that a good linear relationship is obtained between the concentration of the alkaline component of the alkaline developer (hereinafter referred to as " alkali component concentration ") and the conductivity (Hereinafter referred to as " dissolved photoresist concentration ") and the absorbance of the photoresist dissolved in the alkaline developing solution.

However, the alkaline developer easily absorbs carbon dioxide in the air to generate carbonates. At this time, the alkali component having the developing activity in the developer is consumed and reduced. Therefore, in order to maintain and maintain the developing performance of the developing solution with high accuracy, it was necessary to manage the developing solution taking into consideration the influence of the carbon dioxide absorbed in the developing solution on the developing performance.

In order to solve such a problem, Patent Document 2 discloses a method of measuring ultrasonic wave propagation speed, conductivity and absorbance of a developer, measuring the ultrasonic wave propagation speed in the alkali concentration, the carbonate concentration and the dissolved resin concentration, The carbonate concentration and the dissolved resin concentration of the developer are detected on the basis of the measured values (matrix), and the alkali concentration, the carbonate concentration and the dissolved resin concentration of the measured developer, and the CD value (critical dimension value) Based on the relationship between the alkali concentration, the carbonate concentration and the dissolved resin concentration that can exert the dissolving ability to control the alkali concentration by controlling the supply of the developer stock solution.

Patent Document 3 discloses a carbonic acid-based salt concentration measuring device for measuring the refractive index, conductivity and absorbance of a developer and obtaining the concentration of carbonate-based salts in the developer from the measured values, and a device for measuring the concentration of carbonic acid- An alkaline developer management system including a control unit for controlling the concentration of carbonate-based salts in the developer.

Japanese Patent No. 2561578 Japanese Patent Application Laid-Open No. 2008-283162 Japanese Patent Application Laid-Open No. 2011-128455

However, the ultrasound propagation velocity value or the refractive index value of the alkaline developer is a characteristic value indicating the properties of the liquid of the alkaline developer, which is a multi-component system. The characteristic value indicating the property of the whole liquid generally does not correlate only with the concentration of the specific component contained in the liquid. The characteristic value indicating the properties of such a liquid generally has a correlation with each of the concentrations of various components contained in the liquid. Therefore, when calculating the component concentration of the developing solution from the measured value of the characteristic value indicating the property of such liquid, it is preferable that a certain characteristic value is correlated only with a specific component concentration (for example, in a linear relationship) There is a problem in that the concentration of the specific component can not be calculated with sufficient accuracy if the influence of other components on the characteristic value is ignored.

On the other hand, when the characteristic value of the developing solution is a function of the concentration of various components contained in the developing solution, and when the concentration of each component is calculated from the measured value of the developer characteristic value, a plurality of characteristic values are measured, It is necessary to adopt an appropriate calculation method for calculating the concentration of each component from the measured value. However, it is very difficult to appropriately select characteristic values to be measured, and to find an appropriate calculation method capable of accurately calculating the concentration of each component from measured values of characteristic values. Therefore, unless the characteristic value and the calculation method to be measured are appropriate, there is a problem that the concentration of each component can not be calculated with sufficient accuracy.

Further, in a multicomponent liquid, generally, the concentration of a certain component is not independent of the concentration of the other component. In a multicomponent liquid, there is a correlation that when a concentration of a certain component changes, the concentrations of other components change simultaneously. This makes it more difficult to calculate the component concentration with high precision and to manage the developer with high accuracy.

With respect to the concentration of carbon dioxide absorbed in the developing solution (hereinafter referred to as " absorbed carbon dioxide concentration "), an appropriate characteristic value of a developing solution exhibiting a good correlation with this concentration is not known. Conventionally, It was difficult. It is also important to monitor the change in the concentration of absorbed carbon dioxide in the developer to manage the developer.

The present invention has been made to solve the above problems. The present invention relates to a concentration monitoring apparatus capable of measuring the absorbed carbon dioxide concentration of a developer from the density value of a developer in a multi-component system and capable of monitoring changes in the concentration of absorbed carbon dioxide, Or a predetermined management value, in accordance with the amount of the developer.

The concentration monitoring apparatus of a developing solution of the present invention is a device for monitoring the concentration of a developer from the correspondence between the density of the developer and the absorbed carbon dioxide concentration based on the density meter and the density value of the developer exhibiting the alkalinity measured by the density meter And an alarm means for generating an alarm when the absorbed carbon dioxide concentration value of the developer calculated by the calculation means is out of a preset management range.

According to the present invention, since the density meter for measuring the density value having a good correspondence relationship with the absorbed carbon dioxide concentration of the developer is provided, the absorbed carbon dioxide concentration of the developer can be calculated from the density value measured by the density meter, The concentration of the developing solution can be monitored by means of an alarm.

An apparatus for monitoring concentration, comprising: an external output signal terminal for emitting an alarm signal; an alarm device for emitting an alarm sound; a warning lamp for lighting or flashing light; a display device for displaying a warning; And a relay terminal to which the relay terminal is connected.

The developer managing apparatus of the present invention is a device for managing the developer absorbing the developer by using the correspondence between the density of the developer and the absorbed carbon dioxide concentration on the basis of the density meter and the density value of the developer exhibiting the alkalinity measured by the density meter Control means for issuing a control signal to a control valve provided in a pipe for feeding a replenishing liquid replenished to the developing solution so that the carbon dioxide concentration becomes equal to or lower than a predetermined control value or a control value; And an alarm means for issuing an alarm when the density value of the developer measured by the density meter deviates from the density range corresponding to the management range of the preset absorbent carbon dioxide concentration.

According to the present invention, since the amount of the replenishing liquid to be replenished can be known from the density value of the developing solution measured by the density meter by the correspondence between the density of the developing solution and the absorbed carbon dioxide concentration, Or replenishment of the replenishing liquid so as to be equal to or less than the control value can be managed and the concentration of the developer can be monitored by an alarm by the warning means.

The developer managing apparatus of the present invention is a device for managing the concentration of absorbed carbon dioxide of the developer from the correspondence between the density of the developer and the absorbed carbon dioxide concentration on the basis of the density meter and the density value of the developer exhibiting the alkalinity measured by the density meter Based on the absorbed carbon dioxide concentration of the developer calculated by the calculation unit, the concentration of the absorbed carbon dioxide in the developer to be supplied to the developing solution so that the absorbed carbon dioxide concentration of the developer becomes equal to or less than a predetermined management value or a control value And an alarming means for generating an alarm when the absorbed carbon dioxide concentration value of the developer calculated by the computing unit is out of a predetermined management range.

According to the present invention, since the density meter for measuring the density value having a good correspondence relationship with the absorbed carbon dioxide concentration of the developer is provided, the absorbed carbon dioxide concentration of the developer can be calculated from the density value measured by the density meter, The replenishing liquid can be managed by replenishing the replenishing liquid so that the absorbed carbon dioxide concentration becomes a predetermined management value or a management value and the concentration of the developing liquid can be monitored by an alarm by the warning means.

The developer managing apparatus of the present invention is a device for managing the concentration of absorbed carbon dioxide of the developer from the correspondence between the density of the developer and the absorbed carbon dioxide concentration on the basis of the density meter and the density value of the developer exhibiting the alkalinity measured by the density meter Based on the absorbed carbon dioxide concentration of the developer calculated by the calculation means so that the absorbed carbon dioxide concentration of the developer becomes equal to or less than a predetermined management value or a management value And an alarm means for issuing an alarm when the absorbed carbon dioxide concentration value of the developer calculated by the calculation means exceeds a preset control range.

According to the present invention, since the density meter for measuring the density value having a good correspondence relationship with the absorbed carbon dioxide concentration of the developer is provided, the absorbed carbon dioxide concentration of the developer can be calculated from the density value measured by the density meter, The replenishing liquid can be managed by replenishing the replenishing liquid so that the absorbed carbon dioxide concentration becomes a predetermined management value or a management value and the concentration of the developing liquid can be monitored by an alarm by the warning means.

An image forming apparatus comprising: an external output signal terminal for emitting an alarm signal; an alarm device for emitting an alarm sound; a warning lamp for lighting or flashing light; a display device for displaying an alarm; And a relay terminal to which the relay terminal is connected.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to measure the absorbed carbon dioxide concentration of a developer which has conventionally been difficult to measure, and also to monitor the concentration of the developer. It is also possible to supply and replenish the replenishment liquid to the developer so that the absorbed carbon dioxide concentration of the developer is less than or equal to a predetermined control value or a control value based on the measured density value or the calculated absorbed carbon dioxide concentration value.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a graph showing the relationship between the absorbed carbon dioxide concentration and density of a developer. FIG.
2 is a schematic diagram of a developer concentration monitor of the first embodiment.
3 is a schematic diagram of a typical configuration of a vibration density meter.
4 is a schematic diagram of a development processing step including the developer management apparatus of the second embodiment.
5 is a schematic view of a development processing step including the developer management apparatus of the third embodiment.
6 is a schematic diagram of a development processing step including the developer management apparatus of the fourth embodiment.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as appropriate. However, the shape, size, dimensional ratio, relative arrangement, and the like of the apparatuses described in these embodiments are not limited to those shown in the scope of the present invention unless otherwise specified. As a simple explanation example, it is only schematically shown.

In the following description, as a concrete example of the developer, a 2.38 wt% tetramethylammonium hydroxide aqueous solution (hereinafter, referred to as tetramethylammonium hydroxide), which is mainly used in a semiconductor or liquid crystal panel substrate manufacturing process, . However, the developer to which the present invention is applied is not limited to this. Examples of other developing solutions that can be applied to the developer concentration monitoring apparatus or developer management apparatus of the present invention include aqueous solutions of inorganic compounds such as potassium hydroxide, sodium hydroxide, sodium phosphate, and sodium silicate, and aqueous solutions of trimethylmonoethanol ammonium hydroxide Choline), and the like.

In the following description, the component concentrations such as the alkali component concentration, the dissolved photoresist concentration, and the absorbed carbon dioxide concentration are the concentrations according to the weight percent concentration (wt%). The "dissolved photoresist concentration" refers to the concentration when the dissolved photoresist is converted into the amount of photoresist, and the "absorbed carbon dioxide concentration" refers to the concentration when the absorbed carbon dioxide is converted into the amount of carbon dioxide .

In the developing process, the developer is developed by dissolving unnecessary portions of the photoresist film after the exposure process. The photoresist dissolved by the developing solution generates a photoresist salt with the alkali component of the developing solution. Therefore, unless the developer is appropriately managed, as the developing process proceeds, the developer is consumed by the alkaline component having the developing activity and is deteriorated to deteriorate the developing performance. Simultaneously, the dissolved photoresist accumulates as a photoresist salt with the alkali component in the developer.

The photoresist dissolved by the developer shows a surfactant activity in the developer. Therefore, the photoresist dissolved by the developer increases the wettability of the photoresist film provided in the developing process with respect to the developing solution, thereby improving the affinity between the developer and the photoresist film. Therefore, in a developer containing an appropriate photoresist, the developer can be spread evenly through the fine recesses of the photoresist film, so that the development processing of the photoresist film having fine irregularities can be satisfactorily performed.

Further, in the recent developing process, since a large amount of developer is repeatedly used due to the enlargement of the substrate, the chance that the developer is exposed to the air is increasing. However, the alkaline developer absorbs carbon dioxide in the air when exposed to air. The absorbed carbon dioxide generates a carbonate between itself and the alkali component of the developer. For this reason, unless the developer is appropriately managed, the developer is consumed by the absorbed carbon dioxide of the alkaline component having the developing activity and is reduced. At the same time, the absorbed carbon dioxide accumulates as a carbonate with the alkali component in the developer.

The carbonate in the developer has alkalinity in the developer, and therefore has a developing effect. For example, in the case of a 2.38% aqueous solution of TMAH, development is possible if the concentration of carbon dioxide in the developer is about 0.4 wt% or less.

As described above, unlike the conventional recognition that the photoresist dissolved in the developer or the absorbed carbon dioxide is unnecessary for the development, actually contributes to the developing performance of the developer. Therefore, it is necessary to manage the developer to maintain them at an optimum concentration while permitting the developer to be slightly dissolved in the developer, not to control the developer to completely eliminate the dissolved photoresist and the absorbed carbon dioxide.

With respect to these points, the inventor continued the intensive research, and as a result, the following findings were obtained. That is, a relatively good correspondence relationship (linear relationship) can be obtained between the density value of the developing solution and the absorbed carbon dioxide concentration value irrespective of the alkaline component concentration of the developer or the dissolved photoresist concentration. Further, by using the correspondence relationship (linear relationship), it is possible to measure the concentration of absorbed carbon dioxide, which has been difficult conventionally, by measuring the density of the developer with the density meter. In addition, when this correspondence relationship (linear relationship) is used, the absorbed carbon dioxide concentration of the developer can be managed by the replenishment of the replenisher based on the measured density value or the calculated absorbed carbon dioxide concentration value.

The inventor prepared a TMAH aqueous solution having various alkali carrier concentration, dissolved photoresist concentration and absorbed carbon dioxide concentration as a simulated developer sample on the assumption that management of 2.38% TMAH aqueous solution was carried out. The inventors prepared 11 calibration standard solutions in which the alkali component concentration (TMAH concentration), the dissolved photoresist concentration, and the absorbed carbon dioxide concentration were variously changed with the 2.38% TMAH aqueous solution as the basic composition of the developer.

The inventors conducted an experiment to measure the alkaline component concentration (TMAH concentration), the absorbed carbon dioxide concentration, and the density with respect to these simulated developer samples and confirm the correlation between the component concentration and the density.

The measurement was performed by adjusting the temperature of the calibration standard solution to 25.0 캜. In the temperature control, a bottle containing a calibration standard solution is immersed in a constant temperature water bath maintained at about 25 ° C for a long period of time and sampled from the bottle for a long period of time. For the density measurement, a densimeter employing the inherent oscillation method of obtaining the density from the natural frequency measured by exciting the U-shaped flow cell was used. The unit of measured density value is g / cm3.

Table 1 below shows measurement results of the component concentration and density of each sample.

[Table 1]

The concentration of the components in Table 1 was determined by a titration method capable of accurately analyzing the alkali component concentration (TMAH concentration) and the absorbed carbon dioxide concentration, taking into consideration that the aqueous solution of TMAH is strongly alkaline and easily absorbed and deteriorated by absorbing carbon dioxide Separately measured values were used. However, regarding the concentration of the dissolved photoresist, a weight preparation value was used.

Titration is neutralization titration using hydrochloric acid as titration reagent. As a titration apparatus, Mitsubishi used the GT-200 automatic titrator manufactured by Gakuenari Tech.

Fig. 1 shows a graph of the absorbed carbon dioxide concentration and density of each sample shown in Table 1. Fig. This graph is a graph plotting the values of the respective samples, taking the absorbed carbon dioxide concentration (wt%) on the abscissa axis and the density (g / cm 3) on the ordinate axis. At each point plotted, the regression line was determined by the least squares method.

It can be seen from Fig. 1 that the absorbed carbon dioxide concentration of the developer has a good linear relationship with the density of the developer, although the concentration of the alkaline component and the concentration of the dissolved photoresist varies. Based on the experimental results, the inventors of the present invention have found that, by using the corresponding relationship (linear relationship) between the absorbed carbon dioxide concentration and the density of the developer, the absorbed carbon dioxide concentration of the developer can be calculated by measuring the density of the developer .

Therefore, it is possible to realize a concentration monitoring apparatus for a developer using a density meter capable of measuring the absorbed carbon dioxide concentration of the developer by the corresponding relationship (linear relationship) irrespective of the alkali component concentration (TMAH concentration) or the dissolved photoresist concentration It is possible.

Further, in an alkaline developer to be repeatedly used in a development processing step, the alkaline component concentration (TMAH concentration) and the dissolved photoresist concentration are usually managed by the developer management apparatus. Factors which deteriorate the linearity between the density of the developing solution and the concentration of absorbed carbon dioxide are less than those of the simulated sample. Therefore, the concentration monitoring apparatus capable of measuring the absorbed carbon dioxide concentration of the developer according to the present invention can be more suitably used as a part of the developer managing apparatus capable of monitoring or managing the absorbed carbon dioxide concentration.

In addition, since the alkaline developer tends to increase the absorbed carbon dioxide, the absorbed carbon dioxide concentration of the developer is adjusted to a predetermined control value (for example, Or may be managed under a predetermined management value.

1, since the absorbed carbon dioxide concentration and density of the developer have a corresponding relationship (monotonic relationship) to monotone increase, it is preferable that the absorbed carbon dioxide concentration of the developer is made to be equal to or less than a predetermined management value or a management value, Is equal to or smaller than a corresponding predetermined management value or management value. Therefore, when the density value corresponding to the management value of the absorbed carbon dioxide concentration is a control value of density, even if the density of the developer is measured and the density value is controlled to be equal to or lower than the management value or the management value, It is possible to manage the developer so that the carbon dioxide concentration is less than or equal to a predetermined management value or a management value.

Here, the predetermined management value is an upper limit of the concentration value of carbon dioxide in the developing solution which can exhibit the developing performance satisfactorily, and is a concentration value that has been confirmed in advance or a density value corresponding thereto. The same goes for the following description.

Next, specific embodiments will be described with reference to the drawings.

[First Embodiment]

2 is a schematic diagram of a developer concentration monitoring apparatus according to the present embodiment.

The developer concentration monitor device A of the present embodiment includes a measurement section 1, an arithmetic section 2, and an alarm section WD.

The measuring section 1 includes other measuring means (11 to 13 in the figure) for measuring a density meter for measuring the density of the developing solution and other characteristic values of the developing solution, a sampling pump 14, And a thermostatic chamber (not shown) for adjusting the temperature to a measurement temperature (for example, 25 DEG C).

In the case where the concentration monitoring apparatus A merely needs to measure the density, the measuring means 11 to 13 of the measuring unit 1 may be provided with a density meter (for example, 11) Measurement means (e.g., 12 and 13) for measuring the value are unnecessary. However, as an apparatus for monitoring the concentration of an alkaline developer, there are many cases where not only the absorbed carbon dioxide concentration but also the concentration of the alkaline component and the concentration of the photoresist dissolved in the developer are measured. Therefore, in FIG. 2, measurement means 11, 12, and 13 including other measurement means necessary for measuring the concentration of the alkali component and the concentration of the dissolved photoresist are described. One of these is density. In the following description of the concentration monitoring apparatus A, the measuring means 11 among the measuring means 11 to 13 in Fig. 2 is referred to as a density measuring apparatus.

The calculation unit 2 includes a calculation block 21 for calculating an absorbed carbon dioxide concentration value from the measured density value. In the calculation block 21, a correspondence relationship (for example, a linear relationship as shown in Fig. 1) between the density of the developer and the absorbed carbon dioxide concentration is input in advance. The calculation block 21 has a function of obtaining a corresponding absorbed carbon dioxide concentration value from the measured density value of the developer. It is preferable that the calculation unit 2 includes display means 22 for displaying the calculated absorbed carbon dioxide concentration. Further, the concentration monitoring device A is connected to the water tank in which the developer is stored by the sampling pipe 15.

A method of measuring the absorbed carbon dioxide by the concentration monitoring apparatus A of the present embodiment will be described. The developing solution is fed into the measuring section 1 by the sampling pump 14. The developer conveyed to the measuring section 1 is first subjected to temperature regulation at a predetermined measurement temperature (for example, 25 DEG C) in a thermostatic chamber. The temperature-adjusted developing solution is sent to the density meter 11 or other measuring means 12, 13. The density meter 11 measures the density of the developer. The other measuring means (12, 13) also measure the characteristic values of the developer. The developer after the measurement is discharged from the outlet side piping 16 to the outside of the concentration monitoring apparatus A. [

The density meter 11 and other measuring means 12 and 13 are connected to the calculating block 21 of the calculating unit 2 by a signal line. Measurement data of the density value of the developer measured by the density meter 11 or the characteristic values of the developer measured by the other measuring means 12 and 13 are sent to the calculation block 21 via the signal line.

The calculation block 21 that receives the measurement data of the density value or other characteristic value of the developing solution calculates the component concentration of the developing solution based on the measurement data. The absorbed carbon dioxide concentration of the developer is calculated using the corresponding relationship between the density of the developer and the absorbed carbon dioxide concentration (for example, a linear relationship as shown in Fig. 1). That is, an absorbed carbon dioxide concentration value corresponding to the measured density value of the developer is obtained from the corresponding relationship between the density of the developer and the absorbed carbon dioxide concentration, and this is taken as the measured value of the absorbed carbon dioxide concentration of the developer.

In this way, the concentration monitoring apparatus A of the developer of the present embodiment can measure the absorbed carbon dioxide concentration of the developer from the correspondence between the density of the developer and the absorbed carbon dioxide concentration, based on the measured value of the density of the developer .

As shown in Fig. 2, the concentration monitoring apparatus A according to the present embodiment may be configured such that the measuring section 1 and the calculating section 2 are configured as a single device, or they may be configured separately. The measurement data measured by the density meter 11 or other measuring means 12 and 13 of the measuring unit 1 is passed to the calculating block 21 of the calculating unit 2. In this case, The measuring section 1 and the calculating section 2 may be connected by a signal line or the like. The measurement data may be wirelessly transmitted and received between the measuring unit 1 and the calculating unit 2. [

The concentration monitoring apparatus A and the measuring section 1 of the present embodiment may be connected to the storage tank so that the developer can be sampled from the storage tank in which the developer is stored. Alternatively, the concentration monitoring apparatus A or the measuring section 1 may be connected to the circulation line of the developing process for circulating the developer, either directly or by bypassing.

In Fig. 2, each of the measuring means 11 to 13 including the density meter is connected in series. However, the connection of each measuring means is not limited to this. But may be a parallel connection, and each of them may be independently provided with a liquid delivery path and measured. The order of measurement of the density meter and other measuring means is not specially specified. It may be measured in an optimum order according to the characteristics of each measurement means.

The sampling pump 14 is not necessarily required in the configuration of the measuring section 1 shown in Fig. When directly connected to the circulation line, it is not necessary to provide the sampling pump 14 in the measuring unit 1. [ In addition, even when the developer is sampled from the storage tank, the sampling pump 14 may not be provided in the measuring unit 1. [ On the other hand, although not shown, it is preferable that the constant temperature bath for adjusting the developer to a predetermined measurement temperature is provided immediately before the measurement means.

The calculation block 21 of the calculation unit 2 may have a function of calculating the concentrations of other components such as the concentration of the alkaline component of the developer and the concentration of the dissolved photoresist in addition to the function of calculating the absorbed carbon dioxide concentration from the measured value of the density . By doing so, it is possible to realize a concentration monitoring apparatus capable of measuring the alkaline component concentration of the developer, the dissolved photoresist concentration, and the absorbed carbon dioxide concentration.

The concentration monitoring apparatus A of the present embodiment is provided with an alarm means WD. The warning means WD can issue an alarm when the absorbed carbon dioxide concentration value of the developer calculated by the calculation unit 2, which is one of the calculation means, deviates from the preset management range.

For example, the management range is previously stored in the calculation unit 2, and the calculation unit 2 determines whether the absorbed carbon dioxide concentration value is out of the management range. It is possible to transmit the information from the operation unit 2 to the alarm means WD and cause the alarm means WD to issue an alarm based on the information.

It is also possible to store the management range in advance in the alarm means WD and to receive the information of the component concentration from the operation unit 2 and to determine whether the absorbed carbon dioxide concentration value is within the control range by the alarm means WD Judge. Based on this determination, an alarm can be issued to the alarm means WD.

As long as the alarm means WD can issue an alarm, the storage means of the management range and the determination means are not particularly limited.

Preferably, the alarm means WD includes an external output signal terminal for emitting an alarm signal, an alarm device for emitting an alarm sound, a warning lamp for lighting or flashing light, a display device for displaying a warning, And a relay terminal to which the relay terminal is connected.

When the alarm means WD is an external output signal terminal for issuing an alarm signal, the external output signal terminal is connected to a device not shown. When the device receives an alarm signal from the external output signal terminal, it can perform a predetermined operation. For example, if the system includes a concentration monitoring device, the system can be stopped.

If the warning means WD is a warning device emitting an alarm sound or a warning light for turning on or flashing light, the operator who is close to the concentration monitoring device can be alerted. The operator can check the state of the concentration monitoring apparatus and take appropriate action.

In the case where the warning means WD is a display device for displaying a warning, it is also possible to call attention to the operator. Further, when the display device is electrically connected to the arithmetic unit 2 by wire or wirelessly, the operator who is away from the concentration monitoring device can also be warned.

When the alarm means WD is a relay terminal for switching the opening and closing of the contact, ON and OFF of the device connected to the relay terminal can be switched, and the device can perform a predetermined operation.

As the density meter 11 of the concentration monitor apparatus A of the present embodiment, a pressure differential density meter using a buoyancy density meter or a pressure difference between two points having different liquid heights, Various density meters such as a gamma ray density meter used can be employed. More preferably, it is preferable to employ a vibratory density meter for detecting the natural frequency of the pipeline filled with the liquid to obtain the density.

Fig. 3 schematically shows a representative configuration of a vibration type density meter.

The measurement unit of the oscillation type densitometer includes a sample cell 51 bent in a U-shape, a thermometer 52 measuring the temperature of the liquid sample in the sample cell 51, a thermostat block 51 surrounding the sample cell 51 54, and a heat insulating material 55 is provided on the outer circumference of the thermostatic block 54. And a Peltier element 53 for adjusting the temperature of the sample is provided in the constant temperature block 54. A vibrator 56 is provided at the tip of the bent portion of the sample cell 51. A detector for detecting the oscillation frequency of the oscillator 56 and a driving unit for exciting the oscillator 56 are disposed close to the oscillator 56 have.

The excited sample cell 51 vibrates at a specific frequency related to the mass of the liquid therein. Since the mass of the liquid in the sample cell 51 can be known by detecting the natural frequency, the density of the liquid is measured from the internal volume of the sample cell 51.

The vibration densitometer is characterized in that a highly sensitive and stable measurement is possible and continuous measurement is possible. The vibratory density meter can be measured under a favorable temperature condition and temperature stability by a thermometer, a temperature adjusting means (Peltier element 53 in FIG. 3) and a heat insulating means (heat insulating material 55 in FIG. 3). In the oscillatory density meter, the density of the sample can be measured only by feeding the sample liquid to the sample cell. When measuring the density, the addition of reagents is unnecessary and there is no waste solution.

The various measurement means (11 to 13), particularly the method of installing the density meter, in the developer concentration monitoring apparatus of the present embodiment is not limited to the embodiment shown in Fig.

There are various measurement principles and measurement methods in the density meter, and there are suitable installation methods for each. When employing a density-type density meter or differential pressure-type density meter as the density meter, it is preferable to provide a density meter so that the rich portion or the probe portion of the density meter is immersed in the reservoir of the developer. In the case of employing a gamma ray density meter, a density meter can be provided directly in the channel through which the developer flows. In the case of employing a vibratory density meter, as shown in FIG. 2, when the storage tank and the density meter are connected by a sampling pipe, the developer can be sampled and continuously measured.

The vibratory density meter is continuous and also suitable for on-line use because the density can be measured only by feeding the developer to the sample cell. Further, it is suitable for stably managing the measurement conditions such as the liquid temperature, and can perform stable and high-sensitivity measurement. The density of the oscillation density for the process can be measured with an accuracy of about 0.001 (g / cm 3). According to the linear relationship in FIG. 1, the concentration monitoring apparatus of the present embodiment measures the concentration of carbon dioxide Precision can be achieved. When the concentration of the alkali component of the developing solution or the concentration of the dissolved photoresist is controlled, the linearity of the density and the absorbed carbon dioxide concentration is improved and the improvement of the measurement accuracy of the density meter can be expected. Therefore, It is expected that the carbon dioxide concentration can be measured with higher accuracy.

The developer concentration monitoring apparatus of the present embodiment can be utilized as a component for managing the absorbed carbon dioxide concentration by utilizing the fact that the absorbed carbon dioxide concentration of the developer can be measured. The control means for supplying and replenishing the replenishing liquid to the developer so that the absorbed carbon dioxide concentration of the developer becomes equal to or less than the predetermined control value or the control value based on the absorbed carbon dioxide concentration of the developer measured by the concentration monitoring device, It is possible to constitute a developer management apparatus capable of managing the absorbed carbon dioxide concentration.

[Second embodiment]

4 is a schematic diagram showing the relationship between the density of the developing solution measured by the density meter and the absorbed carbon dioxide concentration of the developer, . The developing solution management apparatus E is shown together with the developing process facility B, the replenishment liquid storage section C and the circulating stirring mechanism D in a mode connected to the developing process facility B .

First, the developing process facility (B) will be briefly described.

The development process facility B mainly includes a developer storage tank 61, an overflow tank 62, a development chamber hood 64, a roller conveyor 65, a developer shower nozzle 67, and the like. The developing solution is stored in the developer storage tank 61. The developer is supplemented with the replenishing liquid to be compositionally controlled. The developer storage tank 61 is provided with a level gauge 63 and an overflow tank 62 and manages the increase of the liquid amount by replenishing the replenishment liquid. The developer reservoir 61 and the developer shower nozzle 67 are connected to each other by a developer pipe 80. The developer stored in the developer reservoir 61 is sent to the developer shower nozzle 67 through the filter 73 by the circulation pump 72 provided in the developer pipe 80. [ The roller conveyor 65 conveys the substrate 66 provided above the developer storage tank 61 and having the photoresist film formed thereon. The developing solution is dropped from the developer shower nozzle 67. The substrate 66 conveyed by the roller conveyor 65 is wetted by the developing solution by passing through the developer to be dropped. Thereafter, the developer is collected in the developer reservoir 61 and stored again. Thus, the developer is circulated in the developing process and used repeatedly. Further, in the development chamber of the small-size glass substrate, a treatment for preventing the carbon dioxide in the air from being absorbed may be performed by filling the nitrogen gas.

Next, the developer management apparatus E of the present embodiment will be described. The developer managing apparatus E of the present embodiment measures the density of the developer in a density meter and calculates the absorbance of the developer by using the corresponding relationship between the density of the developer and the absorbed carbon dioxide concentration (for example, a linear relationship as shown in Fig. 1) The replenishing liquid is replenished to the developer based on the measured density value so that the carbon dioxide concentration becomes a predetermined management value or a management value or less.

The developing solution management apparatus E includes a measuring unit 1, an arithmetic unit 2, a control unit 3 and an alarm unit WD. The sampling pipe 15 and the outlet pipe 16 constitute a developing solution storage tank (Not shown). The measuring unit 1, the calculating unit 2, and the control unit 3 are connected by a signal line.

The measuring section 1 is provided with a sampling pump 14, a density meter 11 and measuring means 12 and 13 for measuring other characteristic values of the developer. The measuring means 12 and 13 are for measuring, for example, the alkali component concentration of the developer or the dissolved photoresist concentration. The density meter 11 and measuring means 12 and 13 are connected in series to the rear end of the sampling pump 14. The measuring section 1 is preferably provided with temperature adjusting means (not shown) for stabilizing the sampled developer to a predetermined temperature in order to increase the measurement accuracy. At this time, it is preferable that the temperature adjusting means is provided immediately before the measuring means. The sampling pipe 15 is connected to the sampling pump 14 of the measuring unit 1 and the outlet pipe 16 is connected to the pipe at the end of the measuring unit.

The calculation unit 2 includes a calculation block 21 for calculating, for example, the alkali component concentration of the developer and the dissolved photoresist concentration. The calculation block 21 is connected to measurement means 12 and 13 provided in the measurement section 1 by a signal line. The measurement means 12 and 13 and the calculation unit 2 are unnecessary when the developer management apparatus E only needs to have a function of measuring the density of the developer and controlling the absorbed carbon dioxide concentration.

The control unit 3 is connected to the density meter 11 of the measuring unit 1 through a signal line. Further, the control section 3 is connected to the control valves 41 to 43 provided in the piping for feeding the replenishing liquid to the developing solution by a signal line. Although the control valves 41 to 43 are shown as the internal components of the developer management apparatus E in Fig. 4, the control valves 41 to 43 are required as the components of the developer management apparatus E of this embodiment It is not something. The control unit 3 may be in contact with the control valves 41 to 43 so as to control the operation of the control valves 41 to 43 and to replenish the replenishing liquid to the developer. The control valves 41 to 43 may be located outside the developer management apparatus E. [

Next, the operation of the developer management apparatus of the present embodiment will be described.

The developer sampled from the developer storage tank 61 is fed into the measuring section 1 and the temperature is adjusted. The developer is then sent to the density meter 11, and the density value is measured. The density measurement data is sent to the control unit 3.

In the control unit 3, a density management value corresponding to the management value of the absorbed carbon dioxide concentration determined based on the correspondence relationship between the density of developer and the absorbed carbon dioxide concentration (for example, a linear relationship as shown in Fig. 1) is set. The control unit 3 carries out the following control based on the measurement value of the density of the developer received from the measuring unit 1. [

When the absorbed carbon dioxide concentration of the developer is controlled to be a predetermined control value, the following control is performed. That is, the replenishing liquid is replenished to the developer so that the density value of the measured developer becomes the control value of density corresponding to the control value of the absorbed carbon dioxide concentration. Taking into consideration that the developer absorbs carbon dioxide and the absorbed carbon dioxide concentration tends to increase unless the concentration is controlled, the replenishing liquid to be replenished can be replenished with a replenishing liquid which functions to dilute the absorbed carbon dioxide concentration of the developer.

When the absorbed carbon dioxide concentration of the developer is controlled to be equal to or less than a predetermined control value, the following management is performed. That is, since the correspondence relationship between the density of the developing solution and the absorbed carbon dioxide concentration is a monotone increasing relationship as shown in Fig. 1, the concentration of the developer to be measured becomes equal to or less than the control value of density corresponding to the control value of the absorbed carbon dioxide concentration, . The replenishing liquid to be replenished can be replenished with a replenishing liquid which serves to dilute the absorbed carbon dioxide concentration of the developer.

Here, the " predetermined management value " is a management value that is known in advance as the absorbed carbon dioxide concentration value when the developer exhibits optimum developing performance. For example, when evaluating the liquid performance of the developer with the line width or the remaining film thickness obtained by the developing treatment, it is the absorbed carbon dioxide concentration value of the developer which can make these optimal values. The same goes for the following description.

As the management of the absorbed carbon dioxide concentration of the developer, for example, when a 2.38% TMAH aqueous solution is used as the developer, the absorbed carbon dioxide concentration of the developer is preferably controlled to 0.40 (wt%) or less. More preferably 0.25 (wt%) or less.

Further, the developer managing apparatus E usually includes measuring means 12, 13 for measuring the characteristics of the developing solution required for the measurement and management of the alkali component concentration and the dissolved photoresist concentration. The characteristic values of the developing solution measured by the measuring means 12 and 13 are sent to the calculating section 2. [ The calculation unit 2 calculates the concentration of the alkali component and the concentration of the dissolved photoresist from the measured characteristic values of the developer, and sends the result to the control unit 3. The control unit 3 manages the alkali component concentration of the developer and the concentration of the dissolved photoresist in an optimal state based on the measurement result or the calculation result.

Examples of the replenishment liquid replenished to the developer include a stock solution, a fresh solution, and pure water for the developer. These replenishers are intended to dilute the absorbed carbon dioxide concentration of the developer. These replenishing liquids are also used for managing the concentration of the alkali component of the developing solution and the concentration of the dissolved photoresist.

The replenishing liquid is stored in the replenishing liquid storage tanks 91, 92 of the replenishing liquid storing portion (C). The replenishing liquid storage tanks 91 and 92 are connected to a nitrogen gas pipeline 86 having valves 46 and 47 and are pressurized by the nitrogen gas supplied through this pipeline. The replenishing liquid reservoirs 91 and 92 are connected to the replenishing liquid channels 81 and 82, respectively, and the replenishing liquid is fed through the valves 44 and 45, which are normally open. The replenishing liquid channels 81 and 82 and the pure water channel 83 are provided with control valves 41 to 43 and the control valves 41 to 43 are controlled by the control unit 3 for opening and closing. As the control valve is operated, the replenishing liquid stored in the replenishing liquid storage tanks 91 and 92 is pressure-fed, and the pure water is also sent. Thereafter, the replenishing liquid is merged with the circulation agitating mechanism D via the confluent pipeline 84, and is supplied to the developer reservoir 61 and agitated.

When the replenishment liquid stored in the replenishment liquid storage tanks 91 and 92 is reduced by the replenishment, the internal pressure is lowered and the supply amount becomes unstable. Therefore, So that the internal pressure of the storage tanks 91 and 92 is maintained. When the replenishment liquid storage tanks 91 and 92 are empty, the valves 44 and 45 are closed and replaced with a new replenishing liquid storage tank filled with the replenishing replenishment liquid, or the replenished replenishment liquid is refilled into the emptied replenishment liquid storage tanks 91 and 92 .

The control of the control valves 41 to 43 is performed, for example, as follows. When the flow rate at the time of opening the control valve is adjusted, the replenishment amount of the liquid amount to be replenished can be replenished by managing the opening time of the control valve. The control unit 3 issues a control signal to the control valve so as to open the control valve for a predetermined time so that the replenishing liquid of the liquid amount to be supplied flows, based on the measured value of the density and the management value.

The control method may employ various control methods used for controlling the control amount to the target value. In particular, Proportional-Integral (P control), Proportional-Control (Integral Control), Differential Control (Differential Control) Control) is preferable. More preferably, PID control (Proportional-Integral-Differential Control) is suitable.

As described above, the developer managing apparatus according to the present embodiment can manage the absorbed carbon dioxide concentration of the developer by replenishing the replenishing liquid to the developer so that the absorbed carbon dioxide concentration of the developer is less than or equal to the predetermined management value or the management value. In addition, various data and graphs can be displayed by the display means 22.

Further, when the absorbed carbon dioxide concentration is out of the control range by the alarm means WD, an alarm can be issued.

[Third embodiment]

5 is a graph showing the relationship between the concentration of the developing liquid measured by the density meter and the absorbed carbon dioxide concentration from the corresponding relationship between the density of the developing liquid and the concentration of carbon dioxide, FIG. 2 is a schematic view of a developer control device for managing the carbon dioxide concentration of a developer by supplying it. The developing solution management apparatus E is shown together with the developing process facility B, the replenishment liquid storage section C and the circulating stirring mechanism D in a mode connected to the developing process facility B .

The developer managing apparatus of the present embodiment is provided with an operation unit for calculating the absorbed carbon dioxide concentration from the measured value of the developer density and a control unit for controlling the absorbed carbon dioxide concentration of the developer, Which is realized by the developing device.

The developer managing apparatus E of the present embodiment includes a measuring section 1, an arithmetic control section 23, and an alarm means WD. The measuring section 1 is provided with a density meter 11 and other measuring means 12 and 13. The operation control unit 23 includes a calculation block 21 and a control block 31. [

In the measuring section 1, the density value of the sampled developer is measured by the density meter 11. The measured density value is sent to the operation control section 23 by a signal line. In addition, details of the measuring unit 1 are the same as those of the second embodiment and thus will not be described.

Based on the correspondence relationship (for example, the linear relationship in Fig. 1) between the density of the developing solution and the absorbed carbon dioxide concentration, the arithmetic control unit 23 that receives the measured value of the density of the developing solution calculates the density The absorbed carbon dioxide concentration of the corresponding developer is calculated from the measured values. The calculated absorbed carbon dioxide concentration is sent to the control block 31 as a measured value of the absorbed carbon dioxide concentration of the developer.

The arithmetic control unit 23 may be provided with a calculation block for calculating the concentration of the alkaline component of the developer or the concentration of the dissolved photoresist, for example, as the arithmetic function.

The control block 31 sends a control signal to the control valves 41 to 43 so that the absorbed carbon dioxide concentration of the developer is equal to or lower than a predetermined control value or a control value based on the measured absorbed carbon dioxide concentration. Since the developer tends to absorb carbon dioxide and increase its concentration, the control is accomplished by supplying a replenishment liquid which acts to dilute the absorbed carbon dioxide concentration. The details of the control are the same as those in the second embodiment, and therefore will not be described.

As the control function, the control unit 3 may be provided with a control block for controlling, for example, the alkali component concentration of the developer and the dissolved photoresist concentration.

As described above, according to the developer managing apparatus E of the present embodiment, it is possible to manage the absorbed carbon dioxide concentration of the alkaline developer to be equal to or less than a predetermined management value or a management value. Further, when the absorbed carbon dioxide concentration is out of the control range by the alarm means WD, an alarm can be issued.

[Fourth Embodiment]

6 is a graph showing the relationship between the density of the developer measured by the density meter and the absorbed carbon dioxide concentration from the correspondence between the density of the developer and the absorbed carbon dioxide concentration, To thereby manage the absorbed carbon dioxide concentration of the developer. The developing solution management apparatus E is shown together with the developing process facility B, the replenishment liquid storage section C and the circulating stirring mechanism D in a mode connected to the developing process facility B .

The developer management apparatus of the present embodiment is a developer management apparatus of a system in which calculation means for calculating the absorbed carbon dioxide concentration from the measured value of the density of the developer and control means for controlling the absorbed carbon dioxide concentration of the developer are configured separately.

The developer managing apparatus E of the present embodiment includes a measuring section 1, an arithmetic section 2, a control section 3, and an alarm section WD. The measuring section 1 is provided with a density meter 11 and other measuring means 12 and 13. The calculation unit 2 includes a calculation block 21 for calculating the absorbed carbon dioxide concentration in the developer based on the correspondence relationship between the density and the absorbed carbon dioxide concentration (for example, the linear relationship in FIG. 1) from the measured value of the density. The control unit 3 includes a control block 31 for controlling the replenishment of replenishment liquid to the developer so that the absorbed carbon dioxide concentration of the developer becomes equal to or less than a predetermined control value or a control value based on the calculated absorbed carbon dioxide concentration .

In the measuring section 1, the density value of the sampled developer is measured by the density meter 11. The measured density value is sent to the arithmetic unit 2 by a signal line. In addition, the details of the measuring unit 1 are the same as those of the second embodiment, and therefore will not be described.

Based on the correspondence relationship between the density of the developing solution and the absorbed carbon dioxide concentration (for example, the linear relationship in Fig. 1), the calculation unit 2 that has received the measured value of the density of the developing solution measures the density The absorbed carbon dioxide concentration of the corresponding developing solution is calculated. The calculated absorbed carbon dioxide concentration is sent to the control unit 3 as a measured value of the absorbed carbon dioxide concentration of the developer.

The calculation unit 2 may include a calculation block for calculating the concentration of the alkali component of the developer or the concentration of the dissolved photoresist, for example, as the calculation function.

The control unit 3 sends a control signal to the control valves 41 to 43 so that the absorbed carbon dioxide concentration of the developer becomes equal to or lower than a predetermined control value or a control value based on the measured absorbed carbon dioxide concentration. Since the developer tends to absorb carbon dioxide and increase its concentration, the control is accomplished by supplying a replenishment liquid which acts to dilute the absorbed carbon dioxide concentration. The details of the control are the same as those in the second embodiment, and therefore will not be described.

As the control function, the control unit 3 may be provided with a control block for controlling, for example, the alkali component concentration of the developer and the dissolved photoresist concentration.

As described above, according to the developer managing apparatus E of the present embodiment, it is possible to manage the absorbed carbon dioxide concentration of the alkaline developer to be equal to or less than a predetermined management value or a management value. Further, when the absorbed carbon dioxide concentration is out of the control range by the alarm means WD, an alarm can be issued.

Next, modified examples of the developer managing apparatus E of the present embodiment will be described.

4 to 6, the measuring section 1 of the developer managing apparatus shows a developer managing apparatus that is integrally formed with the calculating section 2 and the control section 3. However, the developer managing apparatus E of the present embodiment But it is not limited thereto. The measuring unit 1 may be configured separately from the calculating unit 2 and the control unit 3. [

Since each measuring means 11 to 13 including the density meter has an optimal mounting method in accordance with the measurement principle employed by each of them, for example, the measuring portion 1 may be in-line connected to the developer duct 80, Or may be provided so as to immerse the measurement probe in the developer reservoir 61. The measuring means 11 to 13 may be provided separately from each other. The developer managing apparatus E of the present embodiment can be realized when the measuring units 11 to 13 are mutually communicated so as to be able to exchange measurement data with the calculating unit 2 and the control unit 3. [

Similarly, although FIGS. 4 to 6 show the developing solution management apparatus E of the present embodiment in which the density and other measurement means 11 to 13 are connected in series, the developer management apparatus E of this embodiment is limited to this It does not. The measuring means 11 to 13 may be connected in parallel or may be connected independently of each other. According to the measuring principle employed by each measuring means, when reagent addition is required, each measuring means may have a pipe for it, or, if a waste liquid is required, each measuring means may have a conduit for it. Even if each measuring means is not connected in series, the developer managing apparatus E of the present embodiment can be realized.

The calculation unit 2 of the developer management apparatus E of the present embodiment calculates the concentration of the developer based on the measured value of the density of the developer from the corresponding relationship between the density of the developer and the absorbed carbon dioxide concentration (for example, In addition to the calculation function for calculating the carbon dioxide concentration, other calculation functions may be provided. For example, an arithmetic function for calculating other component concentrations such as a concentration of an alkali component of a developing solution and a concentration of a dissolved photoresist may be provided.

The control section 3 of the developer managing apparatus E of the present embodiment has a control function for controlling the supply of the replenishing liquid to the developer so that the absorbed carbon dioxide concentration of the developer becomes equal to or less than a predetermined control value or a control value, . For example, a control function may be provided for controlling the concentrations of other components such as the alkali component concentration of the developing solution and the dissolved photoresist concentration to be within a control range below a predetermined control value or a control value. The control for this is not limited to the application of the replenishing liquid to the developer, the addition of the control for appropriately linting the developer, the addition of the control for returning the regenerated developer by filtering the impurities with a filter or the like, Is possible.

4 to 6 show a state in which the developer management apparatus E is connected to the replenishment liquid channel 81 so that the control valves 41 to 43 provided in the pipeline for feeding the replenishment liquid to be supplied to the developer are internal components of the developer management apparatus E. [ , 82, and the pure water line 83, but the developer management apparatus E of the present embodiment is not limited to this. The developer management device does not need to have the control valves 41 to 43 as internal components or may not be connected to the conduits 81 to 83 for replenishing the developer with the replenishing liquid.

The control section 3 in the developer management apparatus E and the control valves 41 to 43 provided in the pipeline for replenishing the replenishing liquid are controlled by the control valves 41 to 43, As long as the control signal received by the control unit 3 of the controller 3 is received and controlled. Even if the control valve is not an internal component of the developer management apparatus E, the developer management apparatus E of the present embodiment can be realized.

The control section 3 of the developer management apparatus E may not be integrally formed with the measuring section 1 or the calculating section 2 and may be separate from the measuring section 1 or the calculating section 2. [ The measuring section 1, the calculating section 2, and the controlling section 3 may be present as individual devices. When the measurement data, calculation results, control signals, and the like are communicated with each other by signal lines or the like, the developer managing apparatus E of the present embodiment can be realized.

It is preferable that the function of controlling the absorbed carbon dioxide concentration of the control unit 3 and the function of controlling other components such as the concentration of the alkali component and the concentration of the dissolved photoresist are realized by the common control means, Or may be realized by a means. The replenishing liquid used for the control, the channel and the control valve for conveying the replenishing liquid may be individually prepared for each component of the developer to be controlled, but it is preferable that the replenishing liquid and the control valve are common if they can be used in common.

Although the developer managing apparatus of the present invention is capable of various modifications as described above, it is provided with a density meter, and the correspondence relationship between the density of the developer and the absorbed carbon dioxide concentration (for example, a linear relationship as shown in Fig. 1) The absorbed carbon dioxide concentration of the developer is calculated on the basis of the density value of the developer measured by the density meter or based on the absorbed carbon dioxide concentration value of the developer calculated from the density value of the developer measured by the density meter, And the replenishing liquid is supplied to the developing solution so that the concentration of the replenishing liquid is below the control value or the control value.

As described above, according to the developer managing apparatus of the present invention, the absorbed carbon dioxide concentration of the alkaline developer can be controlled to be less than a predetermined management value or a management value. Therefore, the alkaline developer can be maintained in the state of the absorbed carbon dioxide concentration exhibiting the optimum developing performance, and the desired line width and remaining film thickness can be realized by the developer managing apparatus of the present embodiment.

When the developer management apparatus of the present invention can further manage the alkali component concentration or the dissolved photoresist concentration of the alkaline developer, the concentration of each component of the alkaline developer is controlled to a predetermined state. Therefore, according to the developer managing apparatus of the present invention, compared with the conventional developer managing method in which the absorbed carbon dioxide concentration can not be managed, the development performance of the alkaline developer can be more accurately maintained. Therefore, the developing speed at the time of developing the photoresist is stabilized, the line width and the remaining film thickness by the developing treatment are stabilized, the product quality is improved, and it is expected to contribute to the realization of the miniaturization and high integration of the single layer .

Further, according to the developer managing apparatus of the present invention, since the developer is automatically maintained at the optimum developing performance at all times, it is possible to improve the product yield and eliminate the necessity of the developer replenishing operation, thereby contributing to the reduction of the running cost and the waste liquid cost .

A ... Concentration monitor, B ... Development process equipment, C ... Refill solution reservoir, D ... Circulating stirring device, E ... The developer-
One… Measuring part
11 ... Density meter, 12, 13 ... Measuring means, 14 ... Sampling pump, 15 ... Sampling piping, 16 ... Outlet pipe
2… [0040]
21 ... Operation block, 22 ... Display means
23 ... An arithmetic control unit (e.g., a computer)
3 ... The control unit
31 ... Control block
41 to 43 ... Control valve, 44, 45, 46, 47 ... valve
51 ... Sample cell, 52 ... Thermometer, 53 ... Peltier element, 54 ... Constant temperature block, 55 ... Insulation, 56 ... Oscillator, 61 ... Developer reservoir, 62 ... Overflow tank, 63 ... Level gauge, 64 ... Developing room hood, 65 ... Roller conveyor, 66 ... Substrate, 67 ... Developer nozzle, 71 ... Waste liquid pump, 72, 74 ... Circulation pumps, 73, 75 ... Filter, 80 ... Development pipeline, 81, 82 ... Pipes for replenishment liquids (developer liquid and / or new liquid), 83 ... Pure water pipeline, 84 ... Confluence channel, 85 ... Circulation duct, 86 ... Pipes for nitrogen gas, 91, 92 ... Replenisher storage tank
WD ... Alarm means

Claims (6)

Density meter,
Calculating means for calculating an absorbed carbon dioxide concentration of the developer from the corresponding relationship between the density of the developer and the absorbed carbon dioxide concentration based on the density value of the developer showing the alkalinity measured by the density meter;
And an alarming means for issuing an alarm when the absorbed carbon dioxide concentration value of the developer calculated by the calculation means is out of a preset control range
And a controller for controlling the concentration of the developer. The method according to claim 1,
Wherein the alarm means includes at least one of an external output signal terminal for emitting an alarm signal, an alarm device for emitting an alarm sound, a warning lamp for lighting or flashing light, a display device for displaying a warning, and a relay terminal for switching the opening / And a developing device for developing the developer. Density meter,
The absorbed carbon dioxide concentration of the developer is less than or equal to a predetermined management value or a management value using the correspondence relationship between the density of the developer and the absorbed carbon dioxide concentration based on the density value of the developer exhibiting the alkalinity measured by the density meter Control means for issuing a control signal to a control valve provided in a pipe for feeding the replenishment liquid to be supplied to the developer,
When the density value of the developer measured by the density meter deviates from the density range corresponding to the preset management range of the absorbed carbon dioxide concentration determined by the correspondence between the density of the developer and the absorbed carbon dioxide concentration, An alarm means
And a developing device for developing the developer. Density meter,
An operating section for calculating the carbon dioxide concentration of the developer from the corresponding relationship between the density of the developer and the absorbed carbon dioxide concentration based on the density value of the developer exhibiting the alkalinity measured by the density meter; And a control section for issuing a control signal to a control valve provided in a pipe for feeding a replenishing liquid replenished to the developing solution so that the absorbed carbon dioxide concentration of the developing solution becomes a predetermined management value or a management value or less based on the absorbed carbon dioxide concentration of the developer Control means,
And an alarming means for issuing an alarm when the absorbed carbon dioxide concentration value of the developer calculated by the calculation unit is out of a preset control range
And a developing device for developing the developer. Density meter,
Calculating means for calculating an absorbed carbon dioxide concentration of the developer from the corresponding relationship between the density of the developer and the absorbed carbon dioxide concentration based on the density value of the developer showing the alkalinity measured by the density meter;
A control valve provided in a channel for feeding a replenishing liquid replenished to the developing solution so that the absorbed carbon dioxide concentration of the developing solution becomes equal to or lower than a predetermined control value or a control value based on the absorbed carbon dioxide concentration of the developer calculated by the calculating means Control means for generating a signal,
And an alarming means for issuing an alarm when the absorbed carbon dioxide concentration value of the developer calculated by the calculation means is out of a preset control range
And a developing device for developing the developer. 6. The method according to any one of claims 3 to 5,
Wherein the alarm means includes at least one of an external output signal terminal for emitting an alarm signal, an alarm device for emitting an alarm sound, a warning lamp for lighting or flashing light, a display device for displaying a warning, and a relay terminal for switching the opening / And a developer supplying device for supplying developer to the developing device.

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